WO2014115633A1 - Sebum absorption/dispersion film - Google Patents
Sebum absorption/dispersion film Download PDFInfo
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- WO2014115633A1 WO2014115633A1 PCT/JP2014/050663 JP2014050663W WO2014115633A1 WO 2014115633 A1 WO2014115633 A1 WO 2014115633A1 JP 2014050663 W JP2014050663 W JP 2014050663W WO 2014115633 A1 WO2014115633 A1 WO 2014115633A1
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- sebum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/08—Homopolymers or copolymers of acrylic acid esters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
Definitions
- the present invention relates to a sebum-absorbing / diffusing film applied to an article used in such a manner that sebum adheres thereto.
- the present invention relates to a sebum-absorbing diffusion film that covers the surface of a touch panel of a portable device such as a tablet information terminal or a smartphone.
- portable devices such as portable PCs such as notebook personal computers (PCs), tablet information terminals such as electronic books, mobile phones such as smartphones, portable game machines, and portable terminals such as various PDAs (personal digital assistants)
- PCs notebook personal computers
- tablet information terminals such as electronic books
- mobile phones such as smartphones
- portable game machines and portable terminals
- various PDAs personal digital assistants
- Due to the nature of carrying, dirt such as dirt, cosmetics and sebum tends to adhere to the surface. Of these, sebum is difficult to wipe off compared to dust and unsightly because it remains on the surface in the form of fingerprint marks. Depending on the degree, it gives an unclean impression.
- the display display unit comprising a liquid crystal panel or an organic EL panel
- the display content becomes difficult to see and the visibility is lowered.
- touch panel portable devices which have been widely used in recent years, are operated by a user touching a display unit / input unit that also functions as an input unit with a fingertip.
- the problem is remarkable.
- sebum adhesion applies not only to portable devices but also to door knobs, straps, showcases, and the like.
- the present invention was created to solve the above-described conventional problems, and its purpose is to provide a film having a novel function that the film itself removes sebum dirt adhering to the film surface. is there.
- a film used to cover the surface of an article and prevent sebum from adhering to the surface.
- the film is characterized in that sebum adhering to the film surface is absorbed into the film and diffused in the film.
- sebum adhering to the surface of the film is absorbed into the film and diffuses within the film. For this reason, the amount of sebum on the film surface decreases and eventually becomes almost unnoticeable.
- the film surface can be regenerated to the state prior to sebum deposition.
- a sebum-absorbing diffusion film that removes sebum dirt adhering to the film surface by the film itself absorbing it.
- the sebum-absorbing and diffusing film has absorption and diffusibility particularly for sebum, but excludes that it has absorption and diffusibility for dirt other than sebum (for example, sweat, dirt, cosmetics, etc.). is not.
- the haze value of the film is 10% or less.
- a film having a low haze value is excellent in transparency, it is suitable for applications requiring visual recognition of an adherend such as a display surface (display) or a showcase made of a liquid crystal panel or an organic EL panel, for example. .
- the sebum-absorbing and diffusing film contains an acrylic resin.
- the acrylic resin is preferably a thermoplastic acrylic resin.
- the acrylic resin is preferably a cross-linked acrylic resin. This structure can also provide sebum absorption and diffusibility, and can be excellent in surface touch because it is excellent in cohesion.
- the film contains a plasticizer at a ratio of 5 to 150 parts by mass with respect to 100 parts by mass of the acrylic resin. According to such a composition, it is easy to realize a film having excellent sebum absorption and diffusibility.
- a preferred embodiment of the film disclosed herein is used for protecting the display surface of a portable device.
- the film disclosed herein to the protective application of the display surface of a portable device, the sebum absorption / diffusion action of the film is suitably exerted, and the inconvenience that the display content becomes difficult to see due to the adhesion of sebum is avoided. Can be done.
- an article whose surface is covered with any of the sebum-absorbing diffusion films disclosed herein is provided. Since the surface of this article is covered with a sebum-absorbing diffusion film, sebum stains adhering to the film surface can be reduced over time, and the appearance can be improved.
- a portable device in which a surface having a touch panel type display unit / input unit is covered with any of the sebum-absorbing diffusion films disclosed herein. Since the touch panel type display / input unit can be operated by a user touching it directly with a fingertip, sebum dirt tends to adhere to the display surface, and the disadvantage is relatively large.
- the sebum absorbing and diffusing film disclosed herein is preferably applied to portable devices having such a touch panel type display / input unit.
- FIG. 6 is a contrast image showing changes in the state of sebum adhesion immediately after (initial) adhesion and 25 hours after adhesion in Examples 1 to 4.
- FIG. 5 is a comparison image showing changes in the state of attachment of alternative sebum immediately after attachment (initial stage) in Examples 1 to 4 and 25 hours after attachment.
- 10 is a contrast image showing changes in the state of sebum adhesion immediately after (initial) adhesion and 25 hours after adhesion in Examples 5 to 8.
- FIG. 10 is a comparison image showing changes in the adhesion state of alternative sebum immediately after adhesion (initial stage) and 25 hours after adhesion in Examples 5 to 8.
- the sebum-absorbing and diffusing film (hereinafter also simply referred to as film) disclosed herein is a film used to cover the surface of an article and prevent sebum from adhering to the surface.
- a film 10 according to a preferred embodiment is a single layer film as shown in FIG. 1 and is used to cover a surface 1A of an article 1 such as a portable device.
- the film 10 covers the surface 1A of the article 1 to prevent dirt such as sebum from adhering to the surface 1A.
- the film 10 is affixed to the surface 1A of the article 1 with a weak peelable adhesive force (for example, adhesive strength). Further, the surface 10A of the film 10 is exposed on the outer surface.
- the user's sebum adheres to the surface 10A of the film 10 instead of the surface 1A of the article 1.
- the film 10 absorbs sebum (not shown) adhering to the surface 10A of the film 10 in the above-described manner and absorbs the sebum in the film 10 and diffuses the sebum in the film 10 (sebum absorption and diffusion characteristics).
- the sebum 20 adhering to the surface 10A of the film 10 in this way becomes a wiping that spreads if it is wiped off with a rag or the like, and it is not easy to remove at a satisfactory level and is troublesome. It is. Further, for example, when the surface 1A is a portable device display (a display unit made up of a liquid crystal panel or an organic EL panel), it is difficult to see the display content of the display and the visibility may be lowered. In particular, when the surface 1A is a touch panel of a portable device, the contact operation with the fingertip F can be frequently performed, and therefore the degree of adhesion of the sebum 20 can be considerable.
- the film 10 disclosed herein has sebum absorption and diffusion characteristics as described above, the sebum 20 attached to the surface 10A of the film 10 is absorbed into the film 10 as schematically shown in FIG. . Further, it diffuses in the film 10. Therefore, the amount of sebum on the surface 10A of the film 10 decreases by the amount absorbed in the film 10, and finally, the sebum 20 becomes almost unnoticeable on the surface 10A of the film 10. Therefore, the surface 10A of the film 10 can be regenerated to a state before the sebum is attached.
- the sebum-absorbing diffusion film is a transparent film that is attached to the touch panel surface
- the visibility (permeability) of the film itself may be reduced due to the absorption of sebum.
- the amount of sebum that adheres to the surface of the film does not reduce the transparency of the film. That is, it can be considered that the sebum absorption tolerance of the film is large from the viewpoint of transparency. It can also be considered that the transparency of the film is not relatively disturbed by the nature of the sebum itself absorbed into the film.
- the film was arrange
- the film is not limited to a single layer structure, and is a laminated film having a multilayer structure (for example, a structure of two layers or three layers or more) composed of a plurality of films (typically sebum-absorbing diffusion films) having different compositions. Also good.
- a film (sebum-absorbing diffusion film) disclosed herein may be laminated on one side or both sides of a base material (preferably, a sheet-like transparent base material such as a PET sheet).
- At least one surface (preferably, the surface facing the article) of the film disclosed herein may exhibit an adhesive strength of 0.001 N / 25 mm or more as measured based on a 180 ° peel test specified in JIS Z0237. preferable.
- a film is preferably affixed on an article.
- the adhesive strength is more preferably 0.01 N / 25 mm or more, still more preferably 0.02 N / 25 mm or more, and particularly preferably 0.05 N / 25 mm or more.
- the said adhesive force shall be less than 1 N / 25mm from a viewpoint of the peelability after reaching the intended purpose, and the workability
- the adhesive strength is more preferably 0.5 N / 25 mm or less, still more preferably 0.3 N / 25 mm or less, and particularly preferably 0.1 N / 25 mm or less.
- the adhesive strength may be substantially 0 N / 25 mm.
- the adhesive force of the other surface (preferably, the surface exposed to the outer surface) of the film may be the same adhesive force as that of the one surface, but is lower than that of the one surface from the viewpoint of touch comfort. It is preferable to show force.
- the adhesive strength of the other surface may be 0.02 N / 25 mm or less (for example, 0.01 N / 25 mm or less, typically 0.005 N / 25 mm or less).
- the measurement of the adhesive strength is specifically performed according to the following procedure. Cut the film into a rectangular sheet and prepare a test piece.
- the test piece is preferably about 100 to 200 mm in length, and preferably about 15 to 30 mm in width. When the width is not 25 mm, [N / 25 mm] may be calculated (converted) from the ratio of the actual width to 25 mm.
- the test piece may be lined with a polyethylene terephthalate (PET) film having a thickness of about 25 ⁇ m with respect to the surface opposite to the surface to be measured.
- PET polyethylene terephthalate
- the prepared test piece is pasted on a surface to be measured by reciprocating a 2 kg roller on a stainless steel (SUS304) plate. After holding this for 30 minutes in an environment of 23 ° C.
- the adhesive strength [N / 25 mm] is measured under the conditions.
- the tensile tester is not particularly limited, and a conventionally known tensile tester can be used. For example, it can be measured using “Tensilon” manufactured by Shimadzu Corporation.
- the film disclosed herein preferably has a haze value of 15% or less.
- a film having a low haze value is excellent in transparency, it is preferably used for applications requiring visual recognition of an adherend such as a display surface (display) or a showcase made of a liquid crystal panel or an organic EL panel.
- the haze value is more preferably 10% or less, still more preferably 5% or less, and particularly preferably 3% or less.
- the “haze value (%)” refers to the ratio of diffuse transmitted light to total transmitted light when the target film is irradiated with visible light. Also called cloudy price.
- As the haze meter for example, “HAZEMETER HM-150” manufactured by Murakami Color Research Laboratory Co., Ltd. can be used. The same method is adopted in the embodiments described later.
- the film disclosed herein can be formed from a resin composition such as an acrylic resin composition, a rubber composition (eg, a natural rubber composition), a urethane resin composition, or a silicone resin composition.
- the film is preferably formed from a rubber composition or an acrylic resin composition from the viewpoint of adhesion to an adherend and cost, and is formed from an acrylic resin composition from the viewpoint of sebum absorption and diffusibility. It is preferable.
- the film disclosed herein can typically be a viscoelastic body.
- a viscoelastic body exhibiting viscoelasticity at least at normal temperature (typically 23 ° C., preferably 0 to 40 ° C., more preferably ⁇ 20 to 50 ° C.) is preferable.
- Such a viscoelastic body tends to form a sebum-absorbing diffusion film.
- the viscoelastic body has a storage elastic modulus (G ′) and a loss at the above temperature (typically 23 ° C., preferably 0 to 40 ° C., more preferably ⁇ 20 to 50 ° C.).
- the elastic modulus (G ′′) satisfies G ′> G ′′.
- the storage elastic modulus of the viscoelastic body is preferably 1 MPa or less, and more preferably 0.9 MPa or less.
- the storage elastic modulus (G ′) and the loss elastic modulus (G ′′) are measured using a conventionally known dynamic viscoelasticity measuring device (for example, “ARES” manufactured by Rheometric Scientific) and punched into a measurement sample (for example, ⁇ 7.9 mm). It may be obtained by measuring a value in a predetermined temperature range (for example, ⁇ 70 ° C. to 100 ° C.) at a temperature rising rate of 5 ° C./min while applying a shear strain of 1 Hz in frequency.
- a predetermined temperature range for example, ⁇ 70 ° C. to 100 ° C.
- the viscoelastic body preferably contains an acrylic resin as a base polymer (the main component of the polymer component, the main film component).
- Acrylic resin is also excellent in transparency.
- the acrylic resin can be synthesized from a monomer raw material containing an alkyl (meth) acrylate having an alkyl group as a main monomer.
- the main monomer refers to a monomer component occupying 50% by mass or more of the total monomer components.
- (meth) acrylate” means acrylate and methacrylate comprehensively.
- (meth) acryloyl” means acryloyl and methacryloyl
- (meth) acryl” generically means acrylic and methacryl.
- R 1 in the above formula is a hydrogen atom or a methyl group.
- R 2 is an alkyl group having 1 to 20 carbon atoms (hereinafter, such a range of the number of carbon atoms may be represented as “C 1-20 ”).
- an alkyl (meth) acrylate having a C 1-14 (for example, C 1-10 ) alkyl group is preferable.
- the alkyl group may be linear or branched.
- alkyl (meth) acrylate having a C 1-20 alkyl group examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth).
- alkyl (meth) acrylates can be used alone or in combination of two or more. Of these, alkyl (meth) acrylates having a C 4-9 alkyl group are preferred. Preferred examples include n-butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), and isononyl acrylate. Among these, BA and 2EHA are more preferable, and 2EHA is particularly preferable.
- the blending ratio of the main monomer in all monomer components is preferably 60% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.
- the upper limit of the mixing ratio of the main monomer is not particularly limited, but is preferably 99% by mass or less (for example, 98% by mass or less, typically 95% by mass or less).
- the acrylic resin may be obtained by polymerizing only the main monomer.
- the monomer raw material used for polymerizing the acrylic resin may contain a submonomer copolymerizable with the main monomer in addition to the main monomer for the purpose of improving various properties such as light peelability.
- the said submonomer shall contain not only a monomer but an oligomer. Examples of such a submonomer include a monomer having a functional group (hereinafter also referred to as a functional group-containing monomer).
- the functional group-containing monomer can be added for the purpose of introducing a crosslinking point into the acrylic resin and increasing the cohesive strength of the acrylic resin.
- Such functional group-containing monomers include carboxyl group-containing monomers, acid anhydride group-containing monomers, hydroxyl group (hydroxyl group) -containing monomers, amide group-containing monomers, amino group-containing monomers, epoxy group (glycidyl group) -containing monomers, alkoxy And group-containing monomers and alkoxysilyl group-containing monomers. These can be used alone or in combination of two or more. Among these, a functional group-containing monomer such as a carboxyl group, a hydroxyl group, or an epoxy group is preferable because a crosslinking point can be suitably introduced into the acrylic resin and the cohesive force of the acrylic resin can be further increased. A group-containing monomer or a hydroxyl group-containing monomer is more preferable.
- carboxyl group-containing monomer examples include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and citracone.
- ethylenically unsaturated dicarboxylic acids such as acids. Of these, acrylic acid and / or methacrylic acid are preferable, and acrylic acid is particularly preferable.
- Examples of the acid anhydride group-containing monomer include acid anhydrides such as the above ethylenically unsaturated dicarboxylic acids such as maleic anhydride and itaconic anhydride.
- Examples of the hydroxyl group (hydroxyl group) -containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Unsaturated alcohols such as hydroxyalkyl (meth) acrylates such as butyl (meth) acrylate, N-methylol (meth) acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether Etc.
- Examples of amide group-containing monomers include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N- Examples include methoxymethyl (meth) acrylamide and N-butoxymethyl (meth) acrylamide.
- Examples of the amino group-containing monomer include aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, and the like.
- Examples of the epoxy group (glycidyl group) -containing monomer include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and allyl glycidyl ether.
- Examples of the alkoxy group-containing monomer include methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate.
- Examples of the alkoxysilyl group-containing monomer include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, and 3- (meth). Examples include acryloxypropylmethyldiethoxysilane.
- the functional group-containing monomer when used as a monomer constituting the acrylic resin, the functional group-containing monomer (preferably a carboxyl group-containing monomer) is 1 to 10% by mass (preferably a carboxyl group-containing monomer) in all monomer components for polymerizing the acrylic resin. For example, 2 to 8% by mass, typically 3 to 7% by mass) is preferable.
- a monomer other than the functional group-containing monomer may be included for the purpose of increasing the cohesive strength of the acrylic resin.
- examples of such monomers include vinyl ester monomers such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene, substituted styrene ( ⁇ -methylstyrene and the like), vinyl toluene, and the like.
- the method for polymerizing the monomer or a mixture thereof is not particularly limited, and a conventionally known general polymerization method can be employed. Examples of such a polymerization method include solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization. Of these, solution polymerization is preferred.
- the mode of polymerization is not particularly limited, and a conventionally known monomer supply method, polymerization conditions (temperature, time, pressure, etc.), and use components other than the monomer (polymerization initiator, surfactant, etc.) can be appropriately selected and carried out. it can.
- the entire monomer mixture may be supplied to the reaction vessel at a time (collective supply), or may be gradually dropped and supplied (continuous supply), or divided into several times for a predetermined time. Each quantity may be supplied (divided supply) every time.
- the monomer or a mixture thereof may be partially or entirely supplied as a solution dissolved in a solvent or a dispersion emulsified in water.
- the polymerization initiator is not particularly limited, and examples thereof include azo initiators such as 2,2′-azobisisobutyronitrile, peroxide initiators such as benzoyl peroxide, and phenyl-substituted ethane. Examples thereof include substituted ethane initiators such as redox initiators in which peroxides such as combinations of peroxides and sodium ascorbate and reducing agents are combined.
- the amount of the polymerization initiator used can be appropriately selected according to the type of polymerization initiator and the type of monomer (composition of the monomer mixture), but is usually 0.005 parts by mass with respect to 100 parts by mass of all monomer components. It is appropriate to select from a range of about 1 part by mass.
- the polymerization temperature can be, for example, about 20 ° C. to 100 ° C. (typically 40 ° C. to 80 ° C.).
- crosslinking agent for the acrylic resin include organic metal salts such as zinc stearate and barium stearate, epoxy crosslinking agents, isocyanate crosslinking agents and the like. You may use an oxazoline type crosslinking agent, an aziridine type crosslinking agent, a metal chelate type crosslinking agent, and a melamine type crosslinking agent. These crosslinking agents may be used alone or in combination of two or more.
- epoxy crosslinking agents and isocyanate crosslinking agents can be suitably crosslinked with a carboxyl group, have good operability (typically light release properties), and are excellent in acid resistance.
- the combined use of an epoxy crosslinking agent and an isocyanate crosslinking agent is particularly preferred.
- the blending amount of the crosslinking agent is not particularly limited, but in order to realize a desired adhesive strength and touch feeling, 0.01 to 10 parts by mass (for example 0.05 to 10 parts by mass) with respect to 100 parts by mass of the base polymer (for example, acrylic resin). 5 parts by mass, typically 0.1 to 5 parts by mass).
- the mass ratio (C E / C I ) is 0.01 to 1 (for example, 0.05 to 0.5, Typically, 0.1 to 0.4) is preferable.
- the solvents used are aliphatic hydrocarbons such as hexane, heptane, and mineral spirits, alicyclic hydrocarbons such as cyclohexane, toluene, xylene, solvent naphtha, tetralin, and dipentene.
- Aromatic hydrocarbons such as butyl alcohol, isobutyl alcohol, cyclohexyl alcohol, 2-methylcyclohexyl alcohol, tridecyl alcohol, etc., esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, acetone, methyl ethyl ketone, etc.
- Ketones are preferred examples.
- the molecular weight (Mw: weight average molecular weight) of the base polymer used (synthesized) (for example, acrylic resin) is not particularly limited. Resin) can be preferably used.
- the thermoplastic resin constituting the film in the technology disclosed herein may be a thermoplastic acrylic resin.
- a typical example is an acrylic block copolymer.
- the acrylic block copolymer one having at least one acrylate block (hereinafter also referred to as Ac block) and at least one methacrylate block (hereinafter also referred to as MAc block) can be preferably used.
- a block copolymer having a structure in which Ac blocks and MAc blocks are alternately arranged is preferable.
- the total number of blocks of the Ac block and the MAc block is preferably 3 or more (for example, 3 to 5).
- alkyl acrylate As a main monomer (that is, a component occupying 50% by mass or more of monomer units constituting the block). Of the monomer units, 75% by mass or more (for example, 90% by mass or more) may be alkyl acrylate.
- the Ac block contained in the acrylic block copolymer in an acrylic block copolymer having two or more Ac blocks, at least one Ac block among them may be used,
- the monomer unit constituting the block may be substantially composed of only one or more (typically one) alkyl acrylate.
- the Ac block may be a copolymer of an alkyl acrylate and another monomer (for example, alkyl methacrylate).
- alkyl acrylate constituting the Ac block examples include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate (BA), isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, n -Hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate (2EHA), nonyl acrylate, isononyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate and the like.
- a constitution in which the monomer constituting the Ac block is substantially BA alone
- a constitution in which 2EHA is alone, a constitution comprising two types of BA and 2EHA, and the like can be preferably employed.
- the MAc block typically has alkyl methacrylate as the main monomer. Of all the monomer components constituting the MAc, 75% by mass or more (for example, 90% by mass or more) may be alkyl methacrylate. In a preferred embodiment, the MAc block contained in the acrylic block copolymer (in the acrylic block copolymer having two or more MAc blocks, at least one MAc block may be used, The monomer unit constituting the block may be substantially composed of only one or more (typically one) alkyl methacrylate. Alternatively, the MAc block may be a copolymer of alkyl methacrylate and another monomer (for example, alkyl acrylate).
- alkyl methacrylate constituting the MAc block examples include alkyl methacrylates having 1 to 20 (preferably 1 to 14) carbon atoms in the alkyl group. Specific examples thereof include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, Examples thereof include n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, isononyl methacrylate, decyl methacrylate, dodecyl methacrylate, stearyl methacrylate and the like.
- 50% by mass or more (75% by mass or more or substantially all of the monomers) constituting the MAc block may have 1 to 1 carbon atoms in the alkyl group.
- 4 alkyl methacrylate preferred alkyl methacrylates include methyl methacrylate (MMA) and ethyl methacrylate (EMA).
- MMA methyl methacrylate
- EMA ethyl methacrylate
- a configuration in which the monomer unit is substantially MMA alone, a configuration in which the monomer unit is EMA alone, a configuration composed of two types of MMA and EMA, and the like can be preferably employed.
- the acrylic block copolymer in the technology disclosed herein is viscous to the A block made of a polymer having a hard structure excellent in cohesion and elasticity, such as AB type, ABA type, ABAB type, and ABABA type. It may be copolymerized such that B blocks made of a polymer having an excellent soft structure are alternately arranged.
- a film containing an acrylic block copolymer having such a structure as a base polymer can be a viscoelastic film in which cohesive force, elasticity and viscosity are highly compatible.
- the viscoelastic body of such a composition can be preferably used as a hot melt viscoelastic body.
- An acrylic block copolymer (ABA type, ABABA type, etc.) having a structure in which A blocks are arranged at both ends of the molecule can be preferably used.
- An acrylic block copolymer having such a structure is preferable because it tends to have a good balance between cohesiveness and thermoplasticity.
- the acrylic block copolymer has two or more A blocks
- the monomer composition, molecular weight (degree of polymerization), structure, etc. of these A blocks may be the same or different.
- the MAc block as described above can be preferably used.
- the B block the Ac block as described above can be preferably adopted.
- the acrylic block copolymer is a triblock copolymer having a MAc block-Ac block-MAc block (ABA type) structure.
- ABA type MAc block-Ac block-MAc block
- such a triblock copolymer in which two MAc blocks have substantially the same monomer composition can be preferably employed.
- the mass of the MAc block contained in the acrylic block copolymer (the total mass thereof when two or more MAc blocks are included) and the mass of the Ac block (there are two or more Ac blocks when including two or more Ac blocks)
- the ratio with respect to the total mass) is not particularly limited, but the mass ratio of MAc block / Ac block is 4/96 to 90/10 (usually 7/93 to 80/20, preferably 10/90 to 70/30, For example, a range of 20/80 to 50/50) is preferable.
- the proportion of the MAc block is large, the adhesive strength is lowered, and light peelability tends to be easily obtained.
- the ratio of the Ac block is large, the sebum absorption diffusibility tends to be improved.
- acrylic block copolymer those having a weight average molecular weight (Mw) of about 3 ⁇ 10 4 to 30 ⁇ 10 4 can be appropriately employed.
- An acrylic block copolymer having an Mw of about 3.5 ⁇ 10 4 to 25 ⁇ 10 4 is preferable, and more preferably 4 ⁇ 10 4 to 20 ⁇ 10 4 (for example, 5 ⁇ 10 4 to 15 ⁇ 10 4 ). . If the Mw of the acrylic block copolymer is too small, for example, the cohesiveness may be easily lowered, or the light peelability may be lowered. If Mw is too large, the acrylic block copolymer tends to be insufficient in thermoplasticity.
- the Mw of the acrylic block copolymer referred to here is obtained by performing gel permeation chromatography (GPC) measurement on a sample prepared by dissolving the copolymer in an appropriate solvent (for example, tetrahydrofuran (THF)).
- GPC gel permeation chromatography
- THF tetrahydrofuran
- the acrylic block copolymer in the technology disclosed herein may be copolymerized with monomers other than alkyl acrylate and alkyl methacrylate (other monomers).
- the other monomers include vinyl compounds having functional groups such as alkoxy groups, epoxy groups, hydroxyl groups, amino groups, amide groups, cyano groups, carboxyl groups, and acid anhydride groups, vinyl esters such as vinyl acetate, styrene, etc.
- vinyl esters such as vinyl acetate, styrene, etc.
- aromatic vinyl compounds and vinyl group-containing heterocyclic compounds such as N-vinylpyrrolidone.
- alkyl acrylates, fluorinated alkyl acrylates and fluorinated alkyl methacrylates having a structure in which a fluorinated alkyl group is bonded to an acryloyl group can be mentioned.
- the other monomers can be used, for example, for the purpose of adjusting film properties (adhesive properties, moldability, etc.), and the content thereof is 20% by mass or less of the total monomer components constituting the acrylic block copolymer ( For example, it is appropriate to set it to 10 mass% or less, typically 5 mass% or less.
- the acrylic block copolymer contains substantially no other monomer.
- Such an acrylic block copolymer can be easily synthesized by a known method (for example, see JP-A Nos. 2001-234146 and 11-323072), or a commercially available product can be easily obtained. It can be obtained.
- the commercially available products include Kuraray's product name “LA polymer” series (for example, product numbers such as LA2140e and LA2250), Kaneka's product name “NABSTAR”, and the like.
- a method for synthesizing the acrylic block copolymer a method utilizing a living polymerization method can be preferably employed.
- the living polymerization method it is possible to synthesize an acrylic block copolymer having excellent thermoplastic properties by maintaining the original weather resistance of the acrylic polymer and controlling the structure unique to the living polymerization method.
- the molecular weight distribution can be controlled narrowly, a lack of cohesiveness due to the presence of low molecular weight components can be suppressed, and a viscoelastic body (and thus a film) excellent in light peelability can be realized.
- the acrylic block copolymer can be used alone or in combination of two or more.
- components other than the acrylic block copolymer may be included as an optional component for the purpose of controlling adhesive properties and the like.
- the optional component include polymers and oligomers other than the acrylic block copolymer.
- the blending amount of these polymers and oligomers (hereinafter also referred to as optional polymers) is suitably 50 parts by mass or less, preferably 10 parts by mass or less, per 100 parts by mass of the acrylic block copolymer. More preferably 5 parts by mass or less.
- the film may be substantially free of polymers other than acrylic block copolymers.
- a plasticizer in the resin composition in the technique disclosed herein.
- Inclusion of a plasticizer improves light peelability. Moreover, since the viscosity of a composition falls, film forming property improves. Furthermore, sebum absorption diffusibility improves by containing a plasticizer.
- plasticizers include dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dibutyl phthalate and the like, or adipates such as dioctyl adipate and diisononyl adipate, or trioctyl trimellitic acid Trimellitic acid esters, sebacic acid esters, and the like. Softeners such as process oil are also included in the plasticizer. These can be used alone or in combination of two or more. Of these, adipic acid esters are preferred.
- the blending amount of the plasticizer is not particularly limited, but is suitably 1 part by mass or more with respect to 100 parts by mass of the base polymer (for example, acrylic resin).
- the amount is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more.
- the blending amount is suitably 150 parts by mass or less, preferably 120 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 70 parts by mass or less, and particularly preferably 50 parts by mass or less. .
- the amount of the plasticizer is 120 parts by mass or less (for example, 30 to 120 parts per 100 parts by mass of the base polymer). (Parts by mass, typically 30 to 100 parts by mass).
- tackifiers In addition to the resin composition (or viscoelastic body or film) in the technology disclosed herein, there are other tackifiers, slipperiness agents, surfactants, chain transfer agents, fillers (inorganic fillers, organic fillers).
- fillers inorganic fillers, organic fillers.
- Various additives known in the field of surface protection films such as anti-aging agents, antioxidants, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, and colorants (pigments, dyes, etc.). it can.
- the types and blending amounts of these additive components that are not essential components may be the same as the usual types and blending amounts in this type of film.
- the forming method is not particularly limited.
- a method of applying (typically applying) the resin composition to a flat substrate using a conventionally known application means such as a die coater or a gravure roll coater and drying it.
- the film can be formed by extruding into a film using a conventionally known extruder.
- the thickness of the film disclosed herein can be appropriately selected according to the purpose and is not particularly limited.
- it may be a film having a thickness of 10 ⁇ m to 10 mm (for example, 10 ⁇ m to 5 mm, typically 10 ⁇ m to 3 mm).
- the thickness of the film is preferably about 10 ⁇ m or more (eg, 30 ⁇ m or more, typically 50 ⁇ m or more).
- the thickness of the film is preferably 1000 ⁇ m or less (for example, 300 ⁇ m or less, typically 100 ⁇ m or less).
- At least one surface of the film may be subjected to various conventionally known surface treatments for the purpose of adjusting the adhesive strength such as application of a silicone release agent and imparting slipperiness.
- the article to which the film disclosed herein is applied is not particularly limited as long as it is used in such a manner that sebum adheres thereto.
- a door knob, a strap, a switch cover, a keyboard cover, a show window glass, a glass table, a showcase, and the like can be given.
- various portable apparatuses are mentioned as a suitable example of the articles
- the portable device refers to a portable device, and is not limited to a specific device. Examples thereof include portable devices such as notebook PCs, tablet information terminals such as electronic books, smartphones and other mobile phones, portable game machines, and PDAs (personal digital assistants) such as electronic notebooks.
- a portable device having such a display surface is a touch panel of the tablet-type information terminal 1 as shown in FIG. 3 as a preferred mode of use of the film disclosed herein, which can be a preferred use of the film disclosed herein.
- the use aspect which covers the surface of 2 is mentioned.
- Such an article typically, an electronic device having a touch panel type display unit / input unit is more likely to adhere to the above-described sebum stain because the user directly touches the display surface with a finger. Therefore, it can be a preferred target for use of the film disclosed herein.
- Specific examples of such articles include televisions, car navigation systems, bank ATMs (Automated) in addition to the portable devices described above. Teller Machine).
- a film B was prepared by applying a solvent-based acrylic resin composition (manufactured by Nitoms Co., Ltd.) used for a commercial product to a flat surface (exfoliated) and then performing an aging treatment at 50 ° C. for 24 hours.
- a solvent-based acrylic resin composition manufactured by Nitoms Co., Ltd.
- ⁇ Preparation of film C> Mix 100 parts (solid content) of a commercially available acrylic block copolymer (thermoplastic acrylic resin A) and 30 parts of a plasticizer (diisononyl adipate: “Monocizer W-242”, product of DIC Corporation). The film C having a thickness of about 50 ⁇ m was produced by extrusion molding.
- a film D was produced in the same manner as the film C except that the amount of the plasticizer was increased to 100 parts with respect to 100 parts (solid content) of the acrylic resin.
- ⁇ Preparation of film E> Mix 100 parts (solid content) of a commercially available acrylic block copolymer (thermoplastic acrylic resin B) and 30 parts of a plasticizer (diisononyl adipate: “Monocizer W-242”, product of DIC Corporation). The film E having a thickness of about 50 ⁇ m was produced by extrusion molding.
- a tablet type information terminal (iPad (trademark): Apple product) was prepared, and its display surface (surface made of aluminosilicate glass) was carefully cleaned with a cleaner, and then the films according to the respective examples were attached side by side.
- the films used in each example are as shown in Table 1.
- Example 1 is a blank and is an adherend exposed surface without a film.
- the protective films F and G are commercially available protective films for tablet-type information terminals that claim that fingerprint marks are difficult to adhere. After visually attaching the same level of sebum or alternative sebum to the display surface of the tablet type information terminal or each film on the display surface, the film was stored at 30 ° C. in a dryer.
- the films according to Examples 2, 4 to 6 were found to have sebum-absorbing and diffusing properties, whereas the conventional films according to Examples 3, 7 and 8 had no film.
- the results were the same as in Example 1, and no sebum absorption / diffusion property was observed. More specifically, as shown in FIG. 6 in the captured images of FIGS. 4 to 9, the film according to Example 2 has less sebum from the film surface than the adjacent Examples 1 and 3. Was clearly recognized.
- FIG. 7 it was clearly recognized that the alternative sebum was reduced from the film surface in the films according to Examples 2 and 4 as compared to the adjacent Examples 1 and 3.
- FIG. 9 in particular, it was clearly recognized that the films according to Examples 5 and 6 had reduced alternative sebum from the film surface as compared with Examples 7 and 8. A similar tendency was observed when sebum was used (FIG. 8).
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Abstract
Description
CH2=CR1COOR2
;で表される化合物を好適に用いることができる。ここで、上記式中のR1は水素原子またはメチル基である。また、R2は炭素原子数1~20のアルキル基(以下、このような炭素原子数の範囲を「C1-20」と表すことがある。)である。粘弾性体の貯蔵弾性率等の観点から、C1-14(例えばC1-10)のアルキル基を有するアルキル(メタ)アクリレートが好ましい。なお、上記アルキル基は直鎖状または分岐状であり得る。 Examples of the alkyl (meth) acrylate include the formula:
CH 2 = CR 1 COOR 2
A compound represented by; can be suitably used. Here, R 1 in the above formula is a hydrogen atom or a methyl group. R 2 is an alkyl group having 1 to 20 carbon atoms (hereinafter, such a range of the number of carbon atoms may be represented as “C 1-20 ”). From the viewpoint of storage elastic modulus of the viscoelastic body, an alkyl (meth) acrylate having a C 1-14 (for example, C 1-10 ) alkyl group is preferable. The alkyl group may be linear or branched.
酸無水物基含有モノマーとしては、例えば無水マレイン酸、無水イタコン酸等の上記エチレン性不飽和ジカルボン酸等の酸無水物等が挙げられる。
ヒドロキシル基(水酸基)含有モノマーとしては、例えば2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート等のヒドロキシアルキル(メタ)アクリレート類、N-メチロール(メタ)アクリルアミド、ビニルアルコール、アリルアルコール、2-ヒドロキシエチルビニルエーテル、4-ヒドロキシブチルビニルエーテル、ジエチレングリコールモノビニルエーテル等の不飽和アルコール類等が挙げられる。
アミド基含有モノマーとしては、例えば(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N-ブチル(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N-メチロールプロパン(メタ)アクリルアミド、N-メトキシメチル(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミド等が挙げられる。
アミノ基含有モノマーとしては、例えばアミノエチル(メタ)アクリレート、N,N-ジメチルアミノエチル(メタ)アクリレート、t-ブチルアミノエチル(メタ)アクリレート等が挙げられる。
エポキシ基(グリシジル基)含有モノマーとしては、例えばグリシジル(メタ)アクリレート、メチルグリシジル(メタ)アクリレート、アリルグリシジルエーテル等が挙げられる。
アルコキシ基含有モノマーとしては、例えばメトキシエチル(メタ)アクリレート、エトキシエチル(メタ)アクリレート等が挙げられる。
アルコキシシリル基含有モノマーとしては、例えば3-(メタ)アクリロキシプロピルトリメトキシシラン、3-(メタ)アクリロキシプロピルトリエトキシシラン、3-(メタ)アクリロキシプロピルメチルジメトキシシラン、3-(メタ)アクリロキシプロピルメチルジエトキシシラン等が挙げられる。 Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and citracone. Examples thereof include ethylenically unsaturated dicarboxylic acids such as acids. Of these, acrylic acid and / or methacrylic acid are preferable, and acrylic acid is particularly preferable.
Examples of the acid anhydride group-containing monomer include acid anhydrides such as the above ethylenically unsaturated dicarboxylic acids such as maleic anhydride and itaconic anhydride.
Examples of the hydroxyl group (hydroxyl group) -containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Unsaturated alcohols such as hydroxyalkyl (meth) acrylates such as butyl (meth) acrylate, N-methylol (meth) acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether Etc.
Examples of amide group-containing monomers include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N- Examples include methoxymethyl (meth) acrylamide and N-butoxymethyl (meth) acrylamide.
Examples of the amino group-containing monomer include aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, and the like.
Examples of the epoxy group (glycidyl group) -containing monomer include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and allyl glycidyl ether.
Examples of the alkoxy group-containing monomer include methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate.
Examples of the alkoxysilyl group-containing monomer include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, and 3- (meth). Examples include acryloxypropylmethyldiethoxysilane.
Teller Machine)等が挙げられる。 The article to which the film disclosed herein is applied is not particularly limited as long as it is used in such a manner that sebum adheres thereto. For example, a door knob, a strap, a switch cover, a keyboard cover, a show window glass, a glass table, a showcase, and the like can be given. Moreover, various portable apparatuses are mentioned as a suitable example of the articles | goods used as the application object of the film disclosed here. Here, the portable device refers to a portable device, and is not limited to a specific device. Examples thereof include portable devices such as notebook PCs, tablet information terminals such as electronic books, smartphones and other mobile phones, portable game machines, and PDAs (personal digital assistants) such as electronic notebooks. Since these are carried and used on a daily basis, dirt such as dust, dirt, cosmetics, and sebum is likely to adhere to them. In addition, depending on the degree of sebum stain adhesion, it may give an unclean impression. Further, some of these portable devices have a display surface such as a liquid crystal display or an organic EL display on the surface made of glass or synthetic resin, for example, and when sebum dirt adheres to the display surface, The displayed information is difficult to see and is not easy to use. A portable device having such a display surface is a touch panel of the tablet-
Teller Machine).
2-エチルヘキシルアクリレート(2EHA)とアクリル酸(AA)とを質量比で2EHA:AA=95:5となるように3つ口フラスコに投入し(溶剤はトルエンを使用した。)、窒素気流下にて、重合開始剤として過酸化ベンゾイルを添加し、60℃に昇温させて2時間反応させ、さらに80℃に昇温して1時間反応させることにより、重量平均分子量(Mw)が凡そ50万~60万のアクリル樹脂の溶液を調製した。次いで、かかるアクリル樹脂溶液のポリマー固形分100部に対し、可塑剤(アジピン酸ジイソノニル:「モノサイザーW-242」、DIC(株)製品)30部と、エポキシ系架橋剤(三菱瓦斯化学社製の「TETRAD-C」)0.1部と、イソシアネート系架橋剤(日本ポリウレタン工業社製「コロネートL」)2部とを混合し、アクリル樹脂組成物を調製した。上記で得られたアクリル樹脂組成物を平坦面(剥離処理済み)に塗付した後、50℃で24時間のエージング処理を行うことにより、約80μmの厚さを有するフィルムAを作製した。 <Preparation of film A>
2-Ethylhexyl acrylate (2EHA) and acrylic acid (AA) were charged into a three-necked flask so that the mass ratio was 2EHA: AA = 95: 5 (the solvent used toluene was used), and under a nitrogen stream. Then, benzoyl peroxide is added as a polymerization initiator, the temperature is raised to 60 ° C. and reacted for 2 hours, and further heated to 80 ° C. and reacted for 1 hour, whereby the weight average molecular weight (Mw) is about 500,000. A solution of ˜600,000 acrylic resins was prepared. Next, with respect to 100 parts of the polymer solid content of the acrylic resin solution, 30 parts of a plasticizer (diisononyl adipate: “Monocizer W-242”, a product of DIC Corporation) and an epoxy crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd.) And 0.1 part of an isocyanate-based cross-linking agent (“Coronate L” manufactured by Nippon Polyurethane Industry Co., Ltd.) was mixed to prepare an acrylic resin composition. After the acrylic resin composition obtained above was applied to a flat surface (peeled), an aging treatment was performed at 50 ° C. for 24 hours to produce a film A having a thickness of about 80 μm.
市販製品に用いられる溶剤系アクリル樹脂組成物(株式会社ニトムズ製)を平坦面(剥離処理済み)に塗付した後、50℃で24時間のエージング処理を行うことによりフィルムBを作製した。 <Preparation of film B>
A film B was prepared by applying a solvent-based acrylic resin composition (manufactured by Nitoms Co., Ltd.) used for a commercial product to a flat surface (exfoliated) and then performing an aging treatment at 50 ° C. for 24 hours.
市販のアクリル系ブロック共重合体(熱可塑性アクリル樹脂A)100部(固形分)と、可塑剤(アジピン酸ジイソノニル:「モノサイザーW-242」、DIC(株)製品)30部とを混合し、押出成形することにより約50μmの厚さを有するフィルムCを作製した。 <Preparation of film C>
Mix 100 parts (solid content) of a commercially available acrylic block copolymer (thermoplastic acrylic resin A) and 30 parts of a plasticizer (diisononyl adipate: “Monocizer W-242”, product of DIC Corporation). The film C having a thickness of about 50 μm was produced by extrusion molding.
可塑剤の配合量を、アクリル樹脂100部(固形分)に対して100部に増量した他はフィルムCと同様にしてフィルムDを作製した。 <Preparation of film D>
A film D was produced in the same manner as the film C except that the amount of the plasticizer was increased to 100 parts with respect to 100 parts (solid content) of the acrylic resin.
市販のアクリル系ブロック共重合体(熱可塑性アクリル樹脂B)100部(固形分)と、可塑剤(アジピン酸ジイソノニル:「モノサイザーW-242」、DIC(株)製品)30部とを混合し、押出成形することにより約50μmの厚さを有するフィルムEを作製した。 <Preparation of film E>
Mix 100 parts (solid content) of a commercially available acrylic block copolymer (thermoplastic acrylic resin B) and 30 parts of a plasticizer (diisononyl adipate: “Monocizer W-242”, product of DIC Corporation). The film E having a thickness of about 50 μm was produced by extrusion molding.
タブレット型情報端末(iPad(商標):アップル社製品)を用意し、その表示面(アルミノケイ酸ガラス製の表面)をクリーナーで念入りにクリーニングした後、各例に係るフィルムを並べて貼り付けた。各例で用いたフィルムは表1に示すとおりである。なお、例1はブランクであり、フィルムなしの被着体露出面である。また、保護フィルムF,Gはいずれも、指紋跡が付着しにくいことを謳い文句としている市販のタブレット型情報端末用保護フィルムである。上記タブレット型情報端末の表示面または表示面上の各フィルムに対して、目視で同程度の皮脂または代替皮脂を付着させた後、乾燥器内にて30℃で保存した。そして、皮脂を付着させてから25時間後における表面状態を目視で観察し、下記の基準で評価した。代替皮脂としては、グリセロールモノオレエート(花王社製の商品名「レオドールMO-60」)を用いた。結果を表1および図4~9に示す。
<評価基準>
◎:表面に付着した皮脂が減少していることがはっきりと認められる。
○:表面における皮脂の付着状態が変化しており、皮脂の減少が認められる。
×:表面における皮脂の付着状態に大きな変化は認められない。 [Evaluation of sebum absorption and diffusion]
A tablet type information terminal (iPad (trademark): Apple product) was prepared, and its display surface (surface made of aluminosilicate glass) was carefully cleaned with a cleaner, and then the films according to the respective examples were attached side by side. The films used in each example are as shown in Table 1. In addition, Example 1 is a blank and is an adherend exposed surface without a film. In addition, the protective films F and G are commercially available protective films for tablet-type information terminals that claim that fingerprint marks are difficult to adhere. After visually attaching the same level of sebum or alternative sebum to the display surface of the tablet type information terminal or each film on the display surface, the film was stored at 30 ° C. in a dryer. And the surface state in 25 hours after attaching sebum was visually observed and evaluated according to the following criteria. As an alternative sebum, glycerol monooleate (trade name “Leodol MO-60” manufactured by Kao Corporation) was used. The results are shown in Table 1 and FIGS.
<Evaluation criteria>
(Double-circle): It is recognized clearly that the sebum adhering to the surface is reducing.
○: The sebum adhesion state on the surface is changed, and a decrease in sebum is observed.
X: A big change is not recognized in the adhesion state of the sebum on the surface.
1A (物品の)表面
2 タッチパネル
10 皮脂吸収拡散フィルム(フィルム)
10A (フィルムの)表面
20 皮脂
1 article (tablet type information terminal)
1A (surface of article) 2
10A (film)
Claims (9)
- 物品の表面を覆って該表面への皮脂の付着を防ぐために用いられるフィルムであって、
前記フィルムは、該フィルム表面に付着した皮脂を該フィルム内に吸収し、かつ該フィルム内にて拡散させることを特徴とする、皮脂吸収拡散フィルム。 A film used to cover the surface of the article and prevent sebum from adhering to the surface;
A sebum absorbing and diffusing film, wherein the film absorbs sebum adhering to the film surface into the film and diffuses the sebum in the film. - ヘイズ値が10%以下である、請求項1に記載の皮脂吸収拡散フィルム。 The sebum-absorbing diffusion film according to claim 1, having a haze value of 10% or less.
- アクリル樹脂を含む、請求項1または2に記載の皮脂吸収拡散フィルム。 The sebum-absorbing and diffusing film according to claim 1 or 2, comprising an acrylic resin.
- 前記アクリル樹脂は熱可塑性アクリル樹脂である、請求項3に記載の皮脂吸収拡散フィルム。 The sebum-absorbing diffusion film according to claim 3, wherein the acrylic resin is a thermoplastic acrylic resin.
- 前記アクリル樹脂は架橋されたアクリル樹脂である、請求項3に記載の皮脂吸収拡散フィルム。 The sebum-absorbing and diffusing film according to claim 3, wherein the acrylic resin is a crosslinked acrylic resin.
- 前記アクリル樹脂100質量部に対して5~150質量部の割合で可塑剤を含む、請求項3~5のいずれかに記載の皮脂吸収拡散フィルム。 The sebum-absorbing and diffusing film according to any one of claims 3 to 5, comprising a plasticizer at a ratio of 5 to 150 parts by mass with respect to 100 parts by mass of the acrylic resin.
- ポータブル機器の表示面を保護するために用いられる、請求項1~6のいずれかに記載の皮脂吸収拡散フィルム。 The sebum-absorbing and diffusing film according to any one of claims 1 to 6, which is used for protecting a display surface of a portable device.
- 請求項1~7のいずれかに記載の皮脂吸収拡散フィルムによって表面が覆われた物品。 An article whose surface is covered with the sebum-absorbing diffusion film according to any one of claims 1 to 7.
- タッチパネル方式の表示部/入力部を有する表面が、請求項1~8のいずれかに記載の皮脂吸収拡散フィルムによって覆われているポータブル機器。
A portable device in which a surface having a touch panel type display unit / input unit is covered with the sebum-absorbing diffusion film according to any one of claims 1 to 8.
Priority Applications (3)
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US14/762,675 US20150361233A1 (en) | 2013-01-25 | 2014-01-16 | Sebum absorption/diffusion film |
KR1020157018374A KR20150109355A (en) | 2013-01-25 | 2014-01-16 | Sebum absorption/dispersion film |
CN201480006071.0A CN105026466B (en) | 2013-01-25 | 2014-01-16 | Sebum absorbs diffusion film |
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JP2013-012472 | 2013-01-25 | ||
JP2013012472A JP6049474B2 (en) | 2013-01-25 | 2013-01-25 | Sebum-absorbing diffusion film |
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PCT/JP2014/050663 WO2014115633A1 (en) | 2013-01-25 | 2014-01-16 | Sebum absorption/dispersion film |
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US (1) | US20150361233A1 (en) |
JP (1) | JP6049474B2 (en) |
KR (1) | KR20150109355A (en) |
CN (1) | CN105026466B (en) |
TW (1) | TWI620661B (en) |
WO (1) | WO2014115633A1 (en) |
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US20190233657A1 (en) * | 2016-10-07 | 2019-08-01 | Nissan Motor Co., Ltd. | Stain disappearing laminate, and image display device and automobile component using said stain disappearing laminate |
Families Citing this family (1)
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WO2017221727A1 (en) * | 2016-06-22 | 2017-12-28 | Dic株式会社 | Heat storage sheet |
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KR20150109355A (en) | 2015-10-01 |
JP6049474B2 (en) | 2016-12-21 |
CN105026466B (en) | 2018-06-01 |
CN105026466A (en) | 2015-11-04 |
US20150361233A1 (en) | 2015-12-17 |
TWI620661B (en) | 2018-04-11 |
TW201441040A (en) | 2014-11-01 |
JP2014144991A (en) | 2014-08-14 |
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